Copyright 1996 by the American Chemical Society VOLUME 100, NUMBER 40, OCTOBER 3, 1996

LETTERS

Photocatalytic Decomposition of NO at 275 K on Titanium Oxides Included within

Y-Zeolite Cavities: The Structure and Role of the Active Sites

Hiromi Yamashita, Yuichi Ichihashi, and Masakazu Anpo*

The design of molecular and/or cluster size catalysts within Unique photocatalytic properties which cannot be realized in
zeolite cavities and frameworks is of special interest because normal catalytic systems can be expected in such modified
zeolites offer unique nanoscaled pore reaction fields, an unusual reaction spaces.2,3 Thus, the well-defined nanopores of zeolites
internal surface topology, and ion-exchange capacities. In fact, can provide one of the most promising reaction space fields
the advantages of using zeolite catalysts having such void for photocatalytic reactions.4,5
shapeselective cavities and channels have already been In recent years, we have reported that Cu+/ZSM-5 zeolite and
established in a number of significant industrial catalytic Ag+/ZSM-5 zeolite catalysts work as efficient photocatalysts
processes.1 Furthermore, the modification of the zeolite cavity for the direct decomposition of NO into N2 and O2 at 275 K,3,6-
spaces is also vital to the design and application of highly 10
in which the highly dispersed Cu+ and Ag+ monomer species
efficient and selective photocatalytic systems for reducing in the zeolite cavities play a significant role as active
global air pollution.
 species in the photocatalytic decomposition of NO: the local
X
charge separation on these electronically excited Cu + and Ag+
Abstract published in AdVance ACS Abstracts, September 15, 1996.
S0022-3654(96)01596-1 CCC: $12.00 1996 American Chemical Society
Department of Applied Chemistry, College of Engineering, Osaka Prefecture UniVersity, Gakuen-cho,
Sakai, Osaka 593, Japan

Mitsuo Hashimoto
Central Technical Research Laboratory, Nippon Oil Company, Ltd., Chidori-cho, Naka-ku,
Yokohama 231, Japan

Catherine Louis and Michel Che

Laboratoire de ReactiVite de Surface, UniVersite P. et M. Curie, UA 1106-CNRS, 4 Place Jussieu, Tour 54,
75252 Paris Cedex 05, France
ReceiVed: May 31, 1996; In Final Form: July 31, 1996 X

Titanium oxide species anchored in the Y-zeolite cavities by an ion-exchange method exhibits a high and
unique photocatalytic reactivity for the direct decomposition of NO into N2, O2, and N2O at 275 K with a high
selectivity for the formation of N2. The in situ photoluminescence and XAFS (XANES and FT-EXAFS)
investigations indicate that the titanium oxide species are highly dispersed in the zeolite cavities and exist in
a tetrahedral coordination. The charge-transfer excited state of the titanium oxide species plays a significant
role in the direct decomposition of NO with a high selectivity for the formation of N 2, while the catalysts
involving the aggregated octahedrally coordinated titanium oxide species show a high selectivity to produce
N2O, being similar to reactions on the powdered TiO2 catalysts.
16042 J. Phys. Chem., Vol. 100, No. 40, 1996 Letters
results in the selective formation of N2 and O2. On the other having different Ti concentrations (1.0 and 10 wt % as TiO2 ,
hand, Courbon and Pichat have investigated the photocatalytic respectively) were prepared by impregnating the Y-zeolite with
decomposition of NO on powdered TiO2 catalysts and found an aqueous solution of TiCl3 (imp-Ti oxide/Y-zeolite). TiO2
that the powdered TiO2 photocatalysts decompose NO into N2O powdered catalysts (JRC-TIO-4: anatase 92%, rutile 8%) were
molecules not into N2 and O2.11 However, the photocatalytic supplied as a standard reference catalyst by the Catalysis
decomposition of NO on highly dispersed titanium oxide Society of Japan. The photocatalytic reactions of NO molecules
species prepared in the nanosize pores of zeolites has yet to be were carried out with the catalysts (150 mg) in a quartz cell with
investigated. a flat bottom (60 mL) connected to a conventional vacuum
Anpo et al. have reported that the highly dispersed titanium system (10-6 Torr range).3 Prior to the photoreactions and
oxide catalyst having a tetrahedral coordination can be prepared spectroscopic measurements, the catalysts were degassed at 725
in the micropores of Vycor glass and have shown that the K for 2 h, heated in O2 at the same temperature for 2 h, and
catalyst exhibits a high and characteristic photocatalytic finally evacuated at 475 K to 10-6 Torr. UV irradiation of the
12-14 catalysts in the presence of NO (7.8 mol) was carried out using
reactivity compared to the bulk TiO2 powder. Highly
dispersed titanium oxides included within zeolite cavities (Ti a 75-W high-pressure Hg lamp (> 280 nm) at 275 K. The
oxide/zeolite) were prepared using an ion-exchange method and reaction products were analyzed by gas chromatography. The
used as the photocatalyst for the direct decomposition of NO at photoluminescence spectra of the catalysts were measured at 77
275 K. The photocatalytic properties of this highly dispersed K using a Shimadzu RF-5000 spectrophotofluorometer. The
titanium oxide catalyst were then compared with titanium oxide UV absorption spectra were recorded with a Shimadzu UV-
catalysts prepared by an impregnation method as well as with 2200A spectrometer at 295 K. The ESR spectra were recorded
bulk TiO2 powder catalysts. at 77 K using a JEOL JES-RE2X spectrometer operating in the
In the present study, we deal with the characterization of these X-band mode. The XAFS spectra (XANES and EXAFS) were
catalysts by means of in situ photoluminescence and XAFS measured at the BL-7C facility of the Photon Factory at the
(XANES and FT-EXAFS) measurements and clarifying the National Laboratory for High-Energy Physics, Tsukuba. The Ti
characteristics of the photocatalytic decomposition reaction of K-edge absorption spectra were recorded in the transmission
NO at 275 K. Special attention has been focused on the mode or fluorescence mode at 295 K. The normalized spectra
relationship between the structure of the titanium oxide species were obtained by a procedure described in previous literature,15
and the reaction selectivity in the photocatalytic decomposition and Fourier transformation was performed on k3-weighted
of NO molecules in order to provide the vital information EXAFS oscillations in the range 3-10 -1. The curve-fitting of
required for the design and application of highly active and the EXAFS data was carried out by employing the iterative
selective photocatalytic systems for the efficient decomposition TABLE 1: Comparisons of Yields of N2 and N2O and Their
of NOx into N2 and O2. Selectivities in the Direct Photocatalytic Decomposition of
NO at 275 K on Various Types of the Ti Oxide/Y-Zeolite
The Ti oxide/Y-zeolite (1.1 wt % as TiO2) catalyst was
Catalysts and the Bulk TiO2 Catalyst
prepared by ion exchange with an aqueous titanium ammonium
oxalate solution using Y-zeolite samples (SiO2/Al2O3 ) 5.5)
supplied by the TOSOH corporation (ex-Ti oxide/Y-zeolite). yields
Furthermore, the other two types of Ti oxide/Y-zeolite catalysts
Letters J. Phys. Chem., Vol. 100, No. 40, 1996 16043

(mol/g of TiO2 h) selectivity (%) Ti major reaction on the bulk TiO2 catalyst as well as on the imp-
content Ti oxide/Yzeolite catalyst. Thus, the results obtained with the
catalysts (wt % as TiO2) N2 N2O total N2 N2O ex-Ti oxide/ Y-zeolites clearly show the large difference in
selectivity as well as efficiency with the imp-Ti oxide/Y-zeolite
ex-Ti/Y 1.1 14 1 15 91 9
imp-Ti/Y 1.0 7 10 17 41 59
and the bulk TiO2 catalyst.
imp-Ti/Y 10 5 22 27 19 81 The absorption spectra of the Ti oxide/Y-zeolite catalysts and
TiO2 powder 2 6 8 25 75 bulk TiO2 catalysts were measured by the UV diffuse
reflectance method. The Ti oxide/Y-zeolite catalysts exhibit
nonlinear least-squares method and the empirical backscattering absorption bands in the wavelength regions of 280-330 nm,
parameter sets extracted from the shell features of titanium shifting into the shorter wavelength regions as compared to the
compounds. bulk TiO2 catalyst. Such a blue-shift in the absorption band of
UV irradiation of the powdered TiO2 and the Ti titanium oxides can be attributed to the size quantization effect
oxide/Yzeolite catalysts prepared by ion-exchange or due to the presence of extremely small Ti oxide particles and/or
impregnation methods in the presence of NO was found to lead the presence of highly unsaturated Ti oxide species having a
to the evolution of N2, O2, and N2O in the gas phase at 275 K tetrahedral coordination.12,14,16 A significant blue-shift in the
with different yields and different product selectivities. The absorption band was observed with the ex-Ti oxide/Y-zeolite
yields of these photoformed N2, O2, and N2O increased linearly Figure 1. XANES (a-c) and FT-EXAFS (A-C) spectra of the ex-Ti
to the UV irradiation time and the reaction immediately stopped oxide/Y-zeolite catalyst (a, A), and the imp-Ti oxide/Y-zeolite catalysts
when irradiation was ceased. The formation of these reaction with Ti content of 1.0 wt % (b, B) and 10 wt % as TiO2 (c, C).
products were not detected in the dark conditions nor in UV TABLE 2: Results of the Curve-Fitting of Ti K-Edge
Ticontent EXAFS Data for the Various Types of the Ti Oxide/ Y-
a b
(wt%asTiO 2) Zeolite Catalysts and the Bulk TiO2 Catalyst
irradiation of the zeolite itself without titanium oxides. After
prolonged UV irradiation, the number of the photoformed N2 catalysts shell R () CN
per total number of Ti ions included within the catalyst
exceeded 1.0. These results clearly indicate that the presence of ex-Ti/Y 1.1 Ti-O 1.78 3.7
both titanium oxides included within the zeolites as well as UV imp-Ti/Y 1.0 Ti-O 1.88 5.1
irradiation light are indispensable for the photocatalytic reaction imp-Ti/Y 10 Ti-O 1.93 5.8
to take place while the direct decomposition of NO to produce Ti(OPri)4 Ti-O 1.76 4
N2, O2, and N2O occurs photocatalytically on the surface of the TiO2 powder Ti-O 1.96 6
titanium oxide catalysts.
The photocatalytic reactivities of various titanium oxide a
catalysts for the direct decomposition of NO are shown in Table Bond distances. b Coordination number.
1. Of special interest is the comparison of the photocatalytic
activities of the Ti oxide/Y-zeolite catalysts with that of the catalyst clearly suggesting that the dispersion of the Ti oxide
widely used bulk TiO2 powdered catalyst. It can be seen that the species on this catalyst is higher than on the catalysts prepared
specific photocatalytic reactivities of the Ti oxide/Y-zeolite by impregnation methods. Thus, a clear relationship can be seen
catalysts which have been normalized for the unit amount of between the reactivity for the photocatalytic decomposition of
TiO2 in the catalysts, are much higher than the bulk TiO2 NO and the magnitude in the blue shift of these catalysts.
catalysts. The XANES spectra of the Ti oxide catalyst at the Ti K-edge
Table 1 also shows the yields of the photoformed N2 and N2O show several well-defined preedge peaks which are related to
(efficiency) and their distribution (selectivity) in the the local structures surrounding the Ti atom. Also, the relative
photocatalytic decomposition of NO on various types of intensities of the preedge peaks provide useful information on
titanium oxide catalysts. From Table 1, it is clear that the the coordination number surrounding the Ti atom. 17-20 The bulk
efficiency and selectivity for the formation of N2 strongly powdered anatase and rutile TiO2 catalysts were found to exhibit
depend on the type of catalyst. The ex-Ti oxide/Y-zeolite three characteristic small preedge peaks which are attributed to
catalyst exhibits a high reactivity and a high selectivity for the the transitions from the 1s core level of Ti to three different
formation of N2 while the formation of N2O is found to be the kinds of molecular orbitals (1t1g, 2t2g, and 3eg). On the other
hand, tetrahedrally coordinated Ti such as Ti(OPri)4 was found Figure 3 shows that the ex-Ti oxide/Y-zeolite catalyst
to exhibit an intense single preedge peak since a regular exhibits a photoluminescence spectrum at around 490 nm by
tetrahedron structure lacks an inversion center. excitation at around 290 nm at 77 K. The observed
Figure 1 shows the XANES spectra of the Ti oxide/Y-zeolite photoluminescence and absorption bands are in good agreement
catalysts. The ex-Ti oxide/Y-zeolite catalyst exhibits an intense with those of the highly dispersed tetrahedrally coordinated
single preedge peak, indicating that the titanium oxide species titanium oxides anchored onto Vycor glass where the absorption
in the zeolite has a tetrahedral coordination. As can be seen in of UV light at around 280 nm brings about an electron transfer
Figure 1b, for the imp-Ti oxide/Y-zeolite catalyst having a from the lattice oxygen (Ol2-) to the titanium ion (Ti4+) to form
small Ti content, the single characteristic preedge peak is rather a charge-transfer
weak, indicating that the catalyst consists of a mixture of
tetrahedrally and octahedrally coordinated titanium oxide
species. On the other hand, the imp-Ti oxide/Y-zeolite catalyst
having a high Ti content exhibits three characteristic weak
preedge peaks due to the presence of the crystalline anatase
TiO2.
Figure 1 also shows the FT-EXAFS spectra of the catalysts,
and all data are given without corrections for phase shifts. Table
2 shows the results obtained by the curve-fitting analysis of the
EXAFS spectra. As shown in Figure 1, all of the catalysts
investigated in the present study exhibit a strong peak at around
1.6 which can be assigned to the neighboring oxygen atoms
Figure 2. ESR spectrum of the Ti3+ ions generated by the
photoreduction of the ex-Ti oxide/Y-zeolite catalyst with H2 at 77 K.
16044 J. Phys. Chem., Vol. 100, No. 40, 1996 Letters
(ESR signal was also recorded at 77 K.)

(Ti-O). The ex-Ti oxide/Y-zeolite catalyst exhibits only Ti-O

peaks, indicating the presence of the isolated titanium oxide
species on the catalyst. From the results shown in Table 2, this
ex-Ti oxide/Y-zeolite catalyst can be seen to consist of the 4-
coordinate titanium ions. In Figure 1B and C, the imp-Ti
oxide/Y-zeolite catalysts exhibit an intense peak at around 2.7
. This peak can be assigned to the neighboring titanium atoms
(Ti-O-Ti) as well as to the Ti-O peak, indicating the aggregation
of the titanium oxide species in these catalysts. Taking the
coordination numbers shown in Table 2 in consideration, the
presence of the aggregated octahedral titanium oxide species
can be suggested with the impregnated catalysts. These XANES
and FT-EXAFS investigations indicate that the ex-Ti oxide/Y-
zeolite catalyst involves only the well-isolated tetrahedral Ti
oxide species, while the imp-Ti oxide/Y-zeolite catalyst Figure 3. Photoluminescence spectrum of the ex-Ti oxide/Y-zeolite
involves the aggregated octahedral Ti oxide species. catalyst (a), its excitation spectrum (EX), and the effect of the addition
To investigate the local structure of the titanium oxide species of NO on the photoluminescence spectrum (b-e). Measured at 77 K,
excitation beam: 290 nm, emission monitored at 490 nm; amounts of
of the catalysts prepared within zeolite cavities, an ESR
added NO: (a) 0.0, (b) 0.2, (c) 0.8, (d) 7.6, (e) 21.3 mol g-1.
technique was incorporated to by monitor the Ti3+ ions which
were formed by the photoreduction of the Ti oxide with H2 at 77
excited state.12-14 Therefore, it can easily be concluded that the
K. In Figure 2, the ESR spectrum of the Ti3+ ions formed in this
observed photoluminescence spectrum is attributed to the
way on the ex-Ti oxide/Y-zeolite catalyst shows only one type
radiative decay process from the thus-formed charge-transfer
of Ti3+ signal with a g value of g ) 1.9781. From the g value
excited state to the ground state of the highly dispersed titanium
and the characteristic shape of the spectrum it can be concluded
oxide species having a tetrahedral coordination.12-14 The lifetime
that the Ti3+ species are present in a tetrahedral
of the charge-transfer excited state was determined to be 54 s,
coordination.21 being much longer than that of the TiO2 powders (nanosecond
The addition of NO onto the ex-Ti oxide/Y-zeolite catalyst order). Such a long lifetime of the charge-transfer excited state
leads to the appearance of a new ESR signal with a g value of of the ex-Ti oxide/Y-zeolite catalyst is well associated with the
g) 2.0015 at 77 K. This new signal can be attributed to the NO presence of highly dispersed homogeneous tetrahedral titanium
species adsorbed on the Ti ions.6,22 UV irradiation of the catalyst oxide species. On the other hand, the impTi oxide/Y-zeolite
having the adsorbed NO species was found to lead to a gradual catalysts did not exhibit any photoluminescence spectrum.
decrease in the intensity of the ESR signal linearly with the UV Thus, these results clearly indicate that the ex-Ti oxide/Y-
irradiation time. After UV irradiation was discontinued, the zeolite catalyst consists of the highly dispersed isolated
intensity of the ESR signal returned to its original level. These tetrahedral titanium oxide species, while the imp-Ti oxide/Y-
changes in the ESR signal of the NO species clearly indicate not zeolite catalysts involve the aggregated octahedral titanium
only that the adsorbed NO species act as reaction precursors but oxide species which do not exhibit any photoluminescence
also that the decomposition of NO proceeds photocatalytically. spectrum, being in agreement with results obtained by XAFS
investigations.
 As shown in Figure 3, the addition of NO onto the ex-Ti (7) Anpo. M.; Nomura, T.; Shioya, Y.; Che, M.; Murphy, D.;
oxide/Y-zeolite catalyst leads to an efficient quenching of the Giamello, E. Proc. 10th Int. Cong. Catal. Guczi, L., Solymosi, F., Tetenyi,
P., Eds.; Akademiai Kiado: Budapest, 1993; p 2155.
photoluminescence spectrum of the catalyst. The lifetime of the
(8) Negishi, N.; Matsuoka, M.; Yamashita, H.; Anpo, M. J. Phys.
charge-transfer excited state was also found to be shortened by Chem. 1993, 97, 5211.
the addition of NO, its extent depending on the amount of NO (9) Yamashita, H.; Matsuoka, M.; Tsuji, K.; Shioya, Y.; Anpo M.;
added. These results indicate not only that the tetrahedrally Che,
coordinated titanium oxide species locate at positions accessible M. J. Phys. Chem. 1996, 100, 397.
to the added NO but also that the added NO easily interacts with (10) Matsuoka, M.; Matsuda, E.; Tsuji, K.; Yamashita H.; Anpo, M.
Chem. Lett. 1995, 375.
the charge-transfer excited state of the species.
(11) Courbon, H.; Pichat, P. J. Chem. Soc., Faraday Trans. 1 1984,
From these results, it can be emphasized that a high 80, 3175.
photocatalytic efficiency and selectivity for the formation of N2 (12) Anpo, M.; Nakaya, H.; Kodama. S.; Kubokawa, Y.; Domen, K.;
in the photocatalytic decomposition of NO was achieved with Onishi, T. J. Phys. Chem. 1985, 90, 1633.
the ex-Ti oxide/Y-zeolite catalyst having highly dispersed (13) Anpo, M.; Chiba, K. J. Mol. Catal. 1992, 74, 207.
isolated tetrahedral titanium oxide species while the formation (14) Yamashita, H.; Ichihashi, Y.; Harada, M.; Stewart, G.; Fox M.
A.; Anpo, M. J. Catal. 1996, 158, 97.
of N2O in the photocatalytic decomposition of NO was found to
(15) Tanaka, T.; Yamashita, H.; Tsuchitani, R.; Funabiki, T.;
proceed on the bulk TiO2 catalysts and on the imp-Ti oxide/ Y- Yoshida,
zeolite catalysts involving aggregated octahedrally coordinated S. J. Chem. Soc., Faraday Trans. 1 1988, 84, 2987.
titanium oxide species. On the isolated tetrahedral titanium (16) Liu, X.; Iu K.; Thomas, J. K. J. Chem. Soc., Faraday Trans.
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species as weak ligands to form the reaction precursors. Under (17) Liu, Z.; Davis, R. J. J. Phys. Chem. 1994, 98, 1253.
UV irradiation the charge-transfer excited complexes of the (18) Bordiga, S.; Coluccia, S.; Lamberti, C.; Marchese, L.; Zecchina,
A.; Boscherini, F.; Buffa, F.; Genoni, F.; Leofanti, G.; Petrini, G.; Vlaic,
oxides, (Ti3+-O-)*, are formed. Within their lifetimes the
G. J. Phys. Chem. 1994, 98, 1253.
electron transfer from the electron trapped center, Ti3+, into the (19) Bonneviot, L.; On, D. T.; Lopez, A. J. Chem. Soc., Chem.
-antibonding orbital of NO takes place, and simultaneously, Commun. 1993, 685.
the electron transfer from the -bonding orbital of another NO (20) Behrens, P.; Felsche, J.; Vetter, S.; Schult-Ekloff, G.; Jaeger, N.
into the trapped hole center, O-, occurs. These electron transfers I.; Niemann, W. J. Chem. Soc., Chem. Commun. 1991, 678.
lead to the direct decomposition of two sets of NO on (Ti3+O-)* (21) Anpo, M.; Shima, T.; Fujii, T.; Suzuki, S.; Che, M. Chem. Lett.
into N2 and O2 under UV irradiation in the presence of NO even 1987, 1997.
(22) Anpo, M.; Yabuta, M.; Kodama S.; Kubokawa, Y. Bull. Chem.
at 275 K. On the other hand, with the aggregated or bulk TiO 2
Soc. Jpn. 1986, 59, 259.
catalysts, the photoformed holes and electrons rapidly separated
from each other with large space distances between the holes JP9615969
and electrons, thus preventing the simultaneous activation of
two NO on the same active sites and resulting in the formation
of N2O and NO2 in place of N2 and O2. The decomposed N and
O species react with NO on different sites to form N2O and NO2,
respectively. Although the study of the detailed mechanism
involving such a local charge separation observed on the highly
dispersed titanium oxide catalysts will be the subject of our
future work, the present study clearly demonstrates that the
titanium oxide species anchored within zeolite cavities are
promising candidates for new and applicable photocatalysts for
the reduction of toxic NOx elements.

Acknowledgment. The present work has been supported in

part by the Grant-in-Aid on Priority-Area-Research on
Photoreaction Dynamics (06239110), Catalytic Chemistry
of Unique Reaction Fields (07242264), and International Joint
Project Research (07044162) of the Ministry of Education,
Science, Sports, and Culture of Japan. M.A. is much indebted
to Osaka Prefecture for the Special Project Research and Tokyo
Ohka Foundation for their financial support, as well as to the
Tosoh Corp. for kindly providing the Y-zeolite samples.

References and Notes

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